CN104530845A - Waterborne single-component transparent anti-corrosion coating based on dual-functionalized nano-SiO2 and preparation method of coating - Google Patents
Waterborne single-component transparent anti-corrosion coating based on dual-functionalized nano-SiO2 and preparation method of coating Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
The invention discloses a waterborne single-component transparent anti-corrosion coating based on dual-functionalized nano-SiO2 particles and a preparation method of the coating. The dual-functionalized nano-SiO2 particles are prepared by introducing double bonds on the surfaces of nano-SiO2 particles, further grafting with di(methacryloyloxyethyl) hydrogen phosphate and a fluorine-containing monomer and simultaneously introducing phosphate groups and fluorocarbon chains on the surfaces of the nanoparticles to prepare the dual-functionalized nano-SiO2 particles; and further polymerizing the dual-functionalized nano-SiO2 particles and an emulsion to obtain dual-functionalized nano-SiO2 hybrid styrene-acrylic emulsion, so that the corrosion resistance of the styrene-acrylic emulsion system is greatly increased. Under the condition that an anti-rust pigment is not added, the emulsion can reach ISO4628-3-2003 Ri 0-level anti-corrosion standard after the emulsion is subjected to salt spray for 500 hours.
Description
Technical field
The present invention relates to macromolecule material preparation area, be specifically related to a kind of based on difunctionalization Nano-meter SiO_2
2the preparation of aqueous one-component transparent anticorrosive paint.
Background technology
The mechanism of action of protective system is the coating by forming even compact, intercepts water, oxygen, ion arrival metallic surface formation corrosion galvanic cell.This requires that protective system has certain water tolerance, compactness and metal surface passivation ability.Traditional protective system take organic solvent as the disperse phase of film-forming resin, along with more and more stricter environmental protection specification, exploitation water-based system is the development trend of protective system, and styrene-acrylic system has because of it study hotspot that excellent weathering resistance and film-forming properties become water-based anticorrosive paint.
In water-based styrene-acrylic coating preparation process, in order to improve the dispersion stabilization of monomer, needing to introduce a large amount of hydroaropic substance, making product there is the shortcomings such as compactness difference, water-intake rate is high, base material sticking power is not enough.In order to make up this defect, in emulsion, usually add iron oxide red, zinc phosphate rust-preventive pigment to improve the corrosion resistance nature of coating.But coating is filled by pigment, cannot be applied to transparent corrosion-resistant field.
Along with the development of emulsion polymerization technology, based on polymerization mechanism, develop the method for modifying of multiple raising water-borne coatings performance, generally can be summarized as two large classes.(1) functional monomers such as self-cross linking monomer, organosilane monomer, phosphate ester monomer, epoxy acrylate monomer, fluoropropenes acid mono are introduced.By the special property of these monomers, improve water-borne coatings owing to introducing the ester bond of facile hydrolysis, and the poor water resistance caused, the problems such as screening ability is not enough.Such as: " coatings industry ", 2010,40 (2), 63-65 pages report with glycidyl methacrylate, acrylamide and fluorochemical monomer modifying cinepazid emulsion, obtained protective system salt spray resistance can reach 240h.Chinese Patent Application No. CN 201210415510.6 discloses one to make epoxy acrylate monomer and the monomer modified ACRYLIC EMULSION of acrylated phosphate by oneself, can realize the phosphatization of base material, and when adding pigment, salt-fog resistant time can reach 1000h.Chinese Patent Application No. CN201210573479.9 discloses with tertiary ethylene carbonate (VV10), butyl acrylate, methyl methacrylate as backbone monomers, introducing glycidyl methacrylate, diacetone-acryloamide(DAA), adipic dihydrazide are self-cross linking monomer structure crosslinking structure, and phosphate ester monomer PAM-200 is the ACRYLIC EMULSION of adhesion promoter.The water-based anticorrosive paint salt-fog resistant time 500h of this emulsion preparation.
(2) Nano-meter SiO_2 is introduced
2particle, by the special property of inorganic nano material, improves the performance of organic high molecular polymer.Chinese Patent Application No. CN201210183942.9 discloses with organosilane (as vinyltrimethoxy silane) modified silicasol, silicon sol finishing is made to have double bond, rear participation ACRYLIC EMULSION in-situ polymerization, prepare the organic-inorganic hybrid structure of nucleocapsid structure, salt-fog resistant time 15-20 days.Similar method of modifying, further can modify nanoparticle.Chinese Patent Application No. CN200710157923.8 discloses and has synthesized fluorosilicone multipolymer with the fluorine-containing alkyl ester of vinylformic acid and vinyl silanes, prepare novel fluorosiloxane copolymer material by sol-gel method again ,-the CF of low surface energy can be introduced in organosilicon systems
3, improve the weather resistance of film.
Two problems is there is with functional monomer modifying cinepazid system.First, the consistency of functional monomer and system is poor, and in the course of the polymerization process, alkoxyl group facile hydrolysis forms silicone hydroxyl and is cross-linked with adjacent emulsion particle the organosilane monomers such as vinyltrimethoxy silane, causes system gel; Organic fluorine monomer is excessively strong due to hydrophobicity, is difficult to pass through hydrophilic surfactant active and enters glue core inside participation polyreaction; Phosphate ester monomer, in acid, has certain surfactivity after neutralization, easily affect the emulsifying agent distribution on emulsion particle surface, cause polymerization stability to decline, water-soluble phosphate monomer easily autohemagglutination in aqueous phase, cannot play modifying function simultaneously.Secondly, functional monomer can only carry out modification to main polymer chain, lacks the bridge linking effect between main chain, cause compactness poor during film forming.With Nano-meter SiO_2
2particle modified styrene-acrylic system can form cross-linking set in film process, improves the compactness of film.But due to SiO
2particle surface contains great amount of hydroxy group, and the water tolerance of system is declined.
Summary of the invention
For above-mentioned prior art problem, the invention provides a kind of based on difunctionalization Nano-meter SiO_2
2the preparation technology of aqueous one-component transparent anticorrosive paint, the present invention implements by following technical scheme:
1. difunctionalization Nano-meter SiO_2
2preparation:
(1) by tetraethoxy (TEOS), ethanol according to m (TEOS): m (ethanol)=1:5-1:10, drop in reactor, ammoniacal liquor regulates pH to 8,20-30 DEG C of reaction 5-10h, the dispersed nano SiO of obtained semi-transparent zone blue-fluorescence
2colloidal sol.
(2) by vinylsiloxane according to m (vinylsiloxane): m (TEOS)=1:5-1:10, add above-mentioned SiO
2in colloidal sol, 20-30 DEG C of reaction 3-5h, the Nano-meter SiO_2 of obtained surface double-bond modification
2colloidal sol.Described vinylsiloxane is one or more in vinyltrimethoxy silane, vinyltriethoxysilane and γ-methacryloxypropyl trimethoxy silane.
(3) at the Nano-meter SiO_2 of above-mentioned surface double-bond modification
2t-butyl hydroperoxide is added in colloidal sol, be warming up to 50-60 DEG C, slowly drip the mixture of phosphoric acid hydrogen two (methylacryoyloxyethyl) ester, fluoroacrylate monomer and DMA, reaction 2-5h, the Nano-meter SiO_2 of obtained surperficial difunctionalization modification
2colloidal sol.Described fluoro acrylic ester is one or more in trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate and dodecafluoroheptyl methacrylate.Described m (phosphoric acid hydrogen two (methylacryoyloxyethyl) ester): m (fluoro acrylic ester)=1.1:1-1.5:1.Described phosphoric acid hydrogen two (methylacryoyloxyethyl) ester and the total mass of fluoro acrylic ester and the mass ratio of vinylsiloxane are 2:1-5:1.Described t-butyl hydroperoxide and DMA mass ratio are 1:1, and its consumption is the 0.5-1wt% of phosphoric acid hydrogen two (methylacryoyloxyethyl) ester and fluoroacrylate monomer total mass
(4) by above-mentioned modified silicasol evaporate to dryness, difunctionalization Nano-meter SiO_2 is pulverized to obtain
2particle.
2. difunctional SiO of the present invention
2particle/phenylpropyl alcohol hybridisation emulsion, its formula consists of:
Its preparation method is:
(1) add the deionized water of 5-10% and the emulsifying agent of 10-15% in the reactor, rotating speed 1000rpm is stirred to and dissolves completely, adds nuclear layer monomer mixture, continues to stir 30min, prepares stratum nucleare pre-emulsion.
(2) add the deionized water of 20-30% in the reactor, the emulsifying agent of 20-35%, rotating speed 1000rpm is stirred to and dissolves completely, adds shell monomers mixture, continues to stir 30min, prepares shell pre-emulsion A.Get 10-20% shell pre-emulsion A, add difunctional SiO in formula
2particle, ultrasonic disperse 20min obtains shell pre-emulsion B.
(3) ammonium persulphate is dissolved in the deionized water of 10-15%, obtains initiator solution.Add the deionized water of 45-65% in the reactor, the emulsifying agent of 50-70% and whole sodium bicarbonate, rotating speed 200-300rpm is stirred to and dissolves completely.Be warming up to 80 DEG C, synchronously drip the initiator solution of stratum nucleare pre-emulsion and 30-40% respectively, a Bi Baowen 30min is complete to monomer reaction, is stratum nucleare emulsion.
(5) in above-mentioned stratum nucleare emulsion, drip the initiator solution of shell pre-emulsion A and 40-50% respectively, treat that shell pre-emulsion A drips complete, drip shell pre-emulsion B.Drip to finish and be warming up to 90 DEG C, drip residue 10-30% initiator solution, insulation 2h, is cooled to 40 DEG C, and ammoniacal liquor regulates pH to 8, and 200 order filter-cloth filtering dischargings obtain dual-functional nanometer SiO
2hydridization styrene-acrylic emulsion.
Described nuclear layer monomer is two or more in vinylbenzene, methyl methacrylate, butyl acrylate, methacrylic acid, Vinylstyrene, cyanacrylate, trimethylolpropane trimethacrylate.
Described shell monomers is two or more in vinylbenzene, methyl methacrylate, butyl acrylate, methacrylic acid, N hydroxymethyl acrylamide, acrylamide, Hydroxyethyl acrylate.
Described emulsifying agent is composite emulsifier, m (anionic emulsifier): m (nonionic emulsifying agent)=1:1-2:1, described anionic emulsifier is sodium lauryl sulphate, one in Sodium dodecylbenzene sulfonate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, allyloxy nonyl phenol propyl alcohol polyoxyethylene ether ammonium sulfate, the one in fatty alcohol-polyoxyethylene ether, polyoxyethylene nonylphenol ether selected by nonionic emulsifying agent.
Beneficial effect of the present invention
The hydrophobic interaction of the crosslinked action of organosilane monomer, the passivation of phosphate ester monomer and fluorine monomer, in emulsion particle structured design process, is integrated in spherical Nano-meter SiO_2 by the present invention
2surface, forms fluorine-containing phosphorous difunctionalization Nano-meter SiO_2
2particle.Formed the organic-inorganic hybrid structure of capsule shape by emulsion polymerization, see accompanying drawing 1.
Phosphate ester monomer and fluorine monomer, by the above-mentioned functional monomer easily causing stability of emulsion polymerization to decline, in ethanol by oxidation-reduction trigger system, by the control of free radical trigger rate, are controllably grafted on nano grain surface by the present invention.Simultaneously owing to including two double bonds in phosphoric acid hydrogen two (methylacryoyloxyethyl) ester structure, can become while introducing bound phosphate groups and connect fluorine monomer and Nano-meter SiO_2
2the bridge of particle, without the need to introducing other many double bond compounds again, simplify the surface tissue of nano particle, improve grafting efficiency, mechanism is shown in Fig. 2.
Dual-functional nanometer SiO prepared by the present invention
2hydridization styrene-acrylic emulsion, owing to the addition of functional nano SiO at shell
2particle, can form crosslinked anchor point by the silicone hydroxyl on surface during film forming.The bound phosphate groups being simultaneously bonded to particle surface can form passivation to base material and improve sticking power, fluorocarbon chain can make up the water tolerance caused owing to introducing silicone hydroxyl and decline, thus form good synergistic effect, significantly improve the corrosion resistance nature of benzene emulsion system.This emulsion can when not adding rust-stabilising pigment, and reach ISO 4628-3-2003Ri 0 grade of Corrosion standards through 500h salt fog, its technical indicator is in table 1.
Table 1 dual-functional nanometer SiO2 hydridization styrene-acrylic emulsion technical indicator
| Project | Index |
| Product appearance | Milky white liquid |
| Dry film outward appearance | Dry film is transparent, bright |
| Build/μm | 25-45 |
| Solid content/% | 48-50 |
| Fu Li ﹝ and is drawn Quan Fa ﹞/level | 1 |
| Pencil hardness/H | 4 |
| Salt spray resistance/720h | ISO-4628-3-2003Ri 0 grade corrosion |
Accompanying drawing explanation
Accompanying drawing 1 is Nano-meter SiO_2
2hydridization styrene-acrylic latex kernel structure TEM Electronic Speculum figure, accompanying drawing 2 is Nano-meter SiO_2
2surface modification mechanism figure.
Specific embodiment
Below in conjunction with embodiment, technical scheme of the present invention is further described, but protection scope of the present invention is not limited to embodiment.
Embodiment 1
Difunctionalization Nano-meter SiO_2
2preparation:
Add 1kg tetraethoxy in the reactor, 5kg ethanol, ammoniacal liquor adjust ph to 8,20 DEG C of reaction 10h obtain the dispersed nano SiO of semi-transparent zone blue-fluorescence
2colloidal sol; Add 0.1kg vinyltrimethoxy silane 20 DEG C reaction 5h again, the Nano-meter SiO_2 of obtained surface double-bond modification
2colloidal sol; Be warming up to 50 DEG C, 1g tertbutyl peroxide is added in above-mentioned double bond modified silicasol, slow dropping 0.11kg phosphoric acid hydrogen two (methylacryoyloxyethyl) ester, 0.09kg Hexafluorobutyl mathacrylate and 1g N, the mixing solutions of accelerine, drip and finish 50 DEG C of reaction 3h, steam ethanol, pulverize to obtain fluorine-containing phosphorous difunctionalization Nano-meter SiO_2
2particle.
The preparation of organic inorganic hybridization emulsion:
(1) stratum nucleare pre-emulsion: add 2.5g sodium lauryl sulphate, 2.5g OP-10,0.3kg deionized water in the reactor, rotating speed 1000rpm is stirred to and dissolves completely, add 0.3kg vinylbenzene, 0.1kg butyl acrylate, 0.1kg cyanacrylate, continue to stir 30min and obtain stratum nucleare pre-emulsion.
(2) shell pre-emulsion: add 5g sodium lauryl sulphate, 5gOP-10,1.2kg deionized water in the reactor, rotating speed 1000rpm is stirred to and dissolves completely, add 1.5kg vinylbenzene, 1.3kg butyl acrylate, 0.1kg methacrylic acid, 0.1kg N hydroxymethyl acrylamide, continue to stir 30min and obtain shell pre-emulsion A.Get 10% shell pre-emulsion A, add 0.5kg difunctionalization Nano-meter SiO_2
2ultrasonic disperse 20min obtains shell pre-emulsion B.
(3) letex polymerization: 10g ammonium persulphate is dissolved in 0.6kg deionized water, obtained initiator solution.Add 17.5g sodium lauryl sulphate in the reactor, 17.5g OP-10,20g sodium bicarbonate, 3.9kg deionized water rotating speed 200rpm be stirred to and dissolve completely.Be warming up to 80 DEG C, synchronously drip stratum nucleare pre-emulsion and 0.18kg initiator solution respectively, a Bi Baowen 30min is complete to monomer reaction.Continue to drip shell pre-emulsion A and 0.24kg initiator solution, treat that shell pre-emulsion A drips complete, drip shell pre-emulsion B.Treat that all monomers drip complete, be warming up to 90 DEG C, drip residue 0.18kg initiator solution, insulation 2h, is cooled to 40 DEG C, and ammoniacal liquor regulates pH to 8, and 200 order filter-cloth filtering dischargings obtain dual-functional nanometer SiO
2hydridization styrene-acrylic emulsion.
Embodiment 2
Difunctionalization Nano-meter SiO_2
2preparation:
Add 1kg tetraethoxy in the reactor, 10kg ethanol, ammoniacal liquor adjust ph to 8,25 DEG C of reaction 8h obtain the dispersed nano SiO of semi-transparent zone blue-fluorescence
2colloidal sol; Add 0.1kg vinyltriethoxysilane, 0.1kg γ-methacryloxypropyl trimethoxy silane 25 DEG C reaction 4h again, the Nano-meter SiO_2 of obtained surface double-bond modification
2colloidal sol; Be warming up to 55 DEG C, 10g tertbutyl peroxide is added in above-mentioned double bond modified silicasol, slow dropping 0.6kg phosphoric acid hydrogen two (methylacryoyloxyethyl) ester, 0.2kg trifluoroethyl methacrylate, 0.2kg Hexafluorobutyl mathacrylate and 10g N, the mixing solutions of accelerine, drip and finish 55 DEG C of reaction 5h, steam ethanol, pulverize to obtain fluorine-containing phosphorous difunctionalization Nano-meter SiO_2
2particle.
The preparation of organic inorganic hybridization emulsion:
(1) stratum nucleare pre-emulsion: add 10g disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, 5g AEO-9,0.4kg deionized water in the reactor, rotating speed 1000rpm is stirred to and dissolves completely, add 0.6kg vinylbenzene, 0.2kg butyl acrylate, 0.1kg Vinylstyrene, 0.1kg trimethylolpropane trimethacrylate, continue to stir 30min and obtain stratum nucleare pre-emulsion.
(2) shell pre-emulsion: add 23.3g disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, 11.6g AEO-9,1.2kg deionized water in the reactor, rotating speed 1000rpm is stirred to and dissolves completely, add 2.1kg vinylbenzene, 1.5kg butyl acrylate, 0.1kg methacrylic acid, 0.1kg N hydroxymethyl acrylamide, 0.2kg hydroxyethyl methylacrylate, continue to stir 30min and obtain shell pre-emulsion A.Get 15% shell pre-emulsion A, add 1kg difunctionalization Nano-meter SiO_2
2ultrasonic disperse 20min obtains shell pre-emulsion B.
(3) letex polymerization: 50g ammonium persulphate is dissolved in 0.6kg deionized water, obtained initiator solution.Add 33.3g disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate in the reactor, 16.6g AEO-9,50g sodium bicarbonate, 1.8kg deionized water rotating speed 200rpm be stirred to and dissolve completely.Be warming up to 80 DEG C, synchronously drip stratum nucleare pre-emulsion and 0.24kg initiator solution respectively, a Bi Baowen 30min is complete to monomer reaction.Continue to drip shell pre-emulsion A and 0.3kg initiator solution, treat that shell pre-emulsion A drips complete, drip shell pre-emulsion B.Treat that all monomers drip complete, be warming up to 90 DEG C, drip residue 0.06kg initiator solution, insulation 2h, is cooled to 40 DEG C, and ammoniacal liquor regulates pH to 8, and 200 order filter-cloth filtering dischargings obtain dual-functional nanometer SiO
2hydridization styrene-acrylic emulsion.
Embodiment 3
Difunctionalization Nano-meter SiO_2
2preparation:
Add 1kg tetraethoxy in the reactor, 8kg ethanol, ammoniacal liquor adjust ph to 8,30 DEG C of reaction 5h obtain the dispersed nano SiO of semi-transparent zone blue-fluorescence
2colloidal sol; Add 0.15kg γ-methacryloxypropyl trimethoxy silane 30 DEG C reaction 5h again, the Nano-meter SiO_2 of obtained surface double-bond modification
2colloidal sol; Be warming up to 60 DEG C, 3.6g tertbutyl peroxide is added in above-mentioned double bond modified silicasol, slow dropping 0.31kg phosphoric acid hydrogen two (methylacryoyloxyethyl) ester, 0.29kg dodecafluoroheptyl methacrylate and 3.6g N, the mixing solutions of accelerine, drip and finish 60 DEG C of reaction 2h, steam ethanol, pulverize to obtain fluorine-containing phosphorous difunctionalization Nano-meter SiO_2
2particle.
The preparation of organic inorganic hybridization emulsion:
(1) stratum nucleare pre-emulsion: add 4.3g allyloxy nonyl phenol propyl alcohol polyoxyethylene ether ammonium sulfate, 2.9gTX-10,0.4kg deionized water in the reactor, rotating speed 1000rpm is stirred to and dissolves completely, add 0.5kg vinylbenzene, 0.2kg butyl acrylate, 0.1kg Vinylstyrene, continue to stir 30min and obtain stratum nucleare pre-emulsion.
(2) shell pre-emulsion: add 10.1g allyloxy nonyl phenol propyl alcohol polyoxyethylene ether ammonium sulfate, 6.7gTX-10,1.25kg deionized water in the reactor, rotating speed 1000rpm is stirred to and dissolves completely, add 1.8kg vinylbenzene, 1.5kg butyl acrylate, 0.2kg methacrylic acid, 0.1kg acrylamide, continue to stir 30min and obtain shell pre-emulsion A.Get 20% shell pre-emulsion A, add 0.6kg difunctionalization Nano-meter SiO_2
2ultrasonic disperse 20min obtains shell pre-emulsion B.
(3) letex polymerization: 30g ammonium persulphate is dissolved in 0.6kg deionized water, obtained initiator solution.Add in the reactor 21.6g allyloxy nonyl phenol propyl alcohol polyoxyethylene ether ammonium sulfate, 14.4g TX-10,20g sodium bicarbonate, 2.75kg deionized water rotating speed 260rpm be stirred to and dissolve completely.Be warming up to 80 DEG C, synchronously drip stratum nucleare pre-emulsion and 0.21kg initiator solution respectively, a Bi Baowen 30min is complete to monomer reaction.Continue to drip shell pre-emulsion A and 0.27kg initiator solution, treat that shell pre-emulsion A drips complete, drip shell pre-emulsion B.Treat that all monomers drip complete, be warming up to 90 DEG C, drip residue 0.12kg initiator solution, insulation 2h, is cooled to 40 DEG C, and ammoniacal liquor regulates pH to 8, and 200 order filter-cloth filtering dischargings obtain dual-functional nanometer SiO
2hydridization styrene-acrylic emulsion.
Claims (9)
1. one kind based on difunctionalization Nano-meter SiO_2
2the preparation method of aqueous one-component transparent anticorrosive paint, it is characterized in that comprising the steps and processing condition:
Difunctionalization Nano-meter SiO_2
2preparation:
(1) by tetraethoxy (TEOS), ethanol according in input reactor, ammoniacal liquor regulates pH to 8,20-30 DEG C of reaction 5-10h, the dispersed nano SiO of obtained semi-transparent zone blue-fluorescence
2colloidal sol.
(2) vinylsiloxane is added above-mentioned SiO
2in colloidal sol, 20-30 DEG C of reaction 3-5h, the Nano-meter SiO_2 of obtained surface double-bond modification
2colloidal sol.
(3) at the Nano-meter SiO_2 of above-mentioned surface double-bond modification
2t-butyl hydroperoxide is added in colloidal sol, be warming up to 50-60 DEG C, slowly drip the mixture of phosphoric acid hydrogen two (methylacryoyloxyethyl) ester, fluoroacrylate monomer and DMA, reaction 2-5h, the Nano-meter SiO_2 of obtained surperficial difunctionalization modification
2colloidal sol.
(4) by above-mentioned modified silicasol evaporate to dryness, difunctionalization Nano-meter SiO_2 is pulverized to obtain
2particle.
Difunctional SiO
2particle/phenylpropyl alcohol hybridisation emulsion, its formula consists of:
Its preparation method is:
(1) add the deionized water of 5-10% and the emulsifying agent of 10-15% in the reactor, rotating speed 1000rpm is stirred to and dissolves completely, adds nuclear layer monomer mixture, continues to stir 30min, prepares stratum nucleare pre-emulsion.
(2) add the deionized water of 20-30% in the reactor, the emulsifying agent of 20-35%, rotating speed 1000rpm is stirred to and dissolves completely, adds shell monomers mixture, continues to stir 30min, prepares shell pre-emulsion A.Get 10-20% shell pre-emulsion A, add difunctional SiO in formula
2particle, ultrasonic disperse 20min obtains shell pre-emulsion B.
(3) ammonium persulphate is dissolved in the deionized water of 10-15%, obtains initiator solution.Add the deionized water of 45-65% in the reactor, the emulsifying agent of 50-70% and whole sodium bicarbonate, rotating speed 200-300rpm is stirred to and dissolves completely.Be warming up to 80 DEG C, synchronously drip the initiator solution of stratum nucleare pre-emulsion and 30-40% respectively, a Bi Baowen 30min is complete to monomer reaction, is stratum nucleare emulsion.
(5) in above-mentioned stratum nucleare emulsion, drip the initiator solution of shell pre-emulsion A and 40-50% respectively, treat that shell pre-emulsion A drips complete, drip shell pre-emulsion B.Drip to finish and be warming up to 90 DEG C, drip residue 10-30% initiator solution, insulation 2h, is cooled to 40 DEG C, and ammoniacal liquor regulates pH to 8, and 200 order filter-cloth filtering dischargings obtain dual-functional nanometer SiO
2hydridization styrene-acrylic emulsion.
2. one according to claim 1 is based on difunctionalization Nano-meter SiO_2
2the preparation method of aqueous one-component transparent anticorrosive paint, it is characterized in that: the mass ratio of positive silicon ethyl ester and ethanol is 1:5-1:10.
3. one according to claim 1 is based on difunctionalization Nano-meter SiO_2
2the preparation method of aqueous one-component transparent anticorrosive paint, it is characterized in that: the mass ratio of vinylsiloxane and tetraethoxy is 1:5-1:10, described vinylsiloxane is one or more in vinyltrimethoxy silane, vinyltriethoxysilane and γ-methacryloxypropyl trimethoxy silane.
4. one according to claim 1 is based on difunctionalization Nano-meter SiO_2
2the preparation method of aqueous one-component transparent anticorrosive paint, it is characterized in that: phosphoric acid hydrogen two (methylacryoyloxyethyl) ester) and the mass ratio of fluoro acrylic ester be 1.1:1-1.5:1, described fluoro acrylic ester is one or more in trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate and dodecafluoroheptyl methacrylate.
5. one according to claim 1 is based on difunctionalization Nano-meter SiO_2
2the preparation method of aqueous one-component transparent anticorrosive paint, it is characterized in that: phosphoric acid hydrogen two (methylacryoyloxyethyl) ester) and the total mass of fluoro acrylic ester and the mass ratio of vinylsiloxane be 2:1-5:1.
6. one according to claim 1 is based on difunctionalization Nano-meter SiO_2
2the preparation method of aqueous one-component transparent anticorrosive paint, it is characterized in that: described t-butyl hydroperoxide and N, accelerine mass ratio is 1:1, and its consumption is the 0.5-1wt% of phosphoric acid hydrogen two (methylacryoyloxyethyl) ester and fluoroacrylate monomer total mass.
7. one according to claim 1 is based on difunctionalization Nano-meter SiO_2
2the preparation method of aqueous one-component transparent anticorrosive paint, it is characterized in that: described emulsifying agent is composite emulsifier, m (anionic emulsifier): m (nonionic emulsifying agent)=1:1-2:1, described anionic emulsifier is sodium lauryl sulphate, one in Sodium dodecylbenzene sulfonate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, allyloxy nonyl phenol propyl alcohol polyoxyethylene ether ammonium sulfate, the one in fatty alcohol-polyoxyethylene ether, polyoxyethylene nonylphenol ether selected by nonionic emulsifying agent.
8. one according to claim 1 is based on difunctionalization Nano-meter SiO_2
2the preparation method of aqueous one-component transparent anticorrosive paint, it is characterized in that: described nuclear layer monomer is two or more in vinylbenzene, methyl methacrylate, butyl acrylate, methacrylic acid, Vinylstyrene, cyanacrylate, trimethylolpropane trimethacrylate.
9. one according to claim 1 is based on difunctionalization Nano-meter SiO_2
2the preparation method of aqueous one-component transparent anticorrosive paint, it is characterized in that: described shell monomers is two or more in vinylbenzene, methyl methacrylate, butyl acrylate, methacrylic acid, N hydroxymethyl acrylamide, acrylamide, Hydroxyethyl acrylate.
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| CN115197587A (en) * | 2022-08-12 | 2022-10-18 | 山东国瓷功能材料股份有限公司 | Phosphorus-containing modifier modified zirconia, preparation method thereof and optical film |
| CN115197587B (en) * | 2022-08-12 | 2024-07-02 | 山东国瓷功能材料股份有限公司 | Phosphor-containing modifier modified zirconia, preparation method thereof and optical film |
| CN115894780A (en) * | 2022-12-31 | 2023-04-04 | 西南石油大学 | High-strength strong-hydrophobic fluorine-containing proppant and preparation method thereof |
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| CN116285678A (en) * | 2023-02-10 | 2023-06-23 | 青岛理工大学 | Preparation method of nano modified styrene-acrylic-siloxane graft copolymer composite emulsion |
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